US5035823A - Refrigerant compositions of 1,11-trifluoroethane - Google Patents
Refrigerant compositions of 1,11-trifluoroethane Download PDFInfo
- Publication number
- US5035823A US5035823A US07/362,385 US36238589A US5035823A US 5035823 A US5035823 A US 5035823A US 36238589 A US36238589 A US 36238589A US 5035823 A US5035823 A US 5035823A
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- US
- United States
- Prior art keywords
- flon
- trifluoroethane
- temperature
- refrigerants
- coefficient
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
Definitions
- This invention relates to a working fluid for a refrigerator, which is called a refrigerant.
- Refrigerants heretofore known include chlorofluoroalkanes, fluoroalkanes, azeotropic compositions thereof and other materials having a similar composition. These are generally called flons or flon refrigerants. Among them, chiefly used at present are dichlorodifluoromethane (hereinafter referred to as "Flon-12”), chlorodifluoromethane (hereinafter called “Flon-22”) and the like. In recent years, however, it has been pointed out that certain kinds of flons released into the atmosphere would destroy the stratospheric ozone layer, thereby inflicting a serious adverse influence on the ecosystem including humans on the earth.
- Flon-12 dichlorodifluoromethane
- Flon-22 chlorodifluoromethane
- coefficient of performance used herein means the ratio of refrigerating capacity to compressing work.
- the refrigerating capacity is the quantity of heat removed per a unit time from the substances being cooled, and the compressing work is the work volume achieved per a unit time by power for operating the refrigerator. Accordingly the coefficient of performance corresponds to the refrigeration efficiency of the refrigerant.
- the present invention therefore, provides a refrigerant comprising 1,1,1-trifluoroethane and either chlorotetrafluoroethane or tetrafluoroethane.
- FIGS. 1 and 2 show graphs illustrating the refrigerating performance of the refrigerants according to the present invention.
- Preferred refrigerant compositions of the invention are those comprising 90 to 5% by weight of 1,1,1-trifluoroethane and 10 to 95% by weight of either chlorotetrafluoroethane or tetrafluoroethane.
- Refrigerants containing chlorotetrafluoroethane or tetrafluoroethane in the foregoing ratio have a noticeably improved coefficient of performance compared with Flon-143a singly used.
- a particularly preferable mixing ratio is as follows. Of refrigerants composed of Flon-143a and chlorotetrafluoroethane, preferred are those comprising 70 to 5% by weight of the former and 30 to 95% by weight of the latter. Of refrigerants composed of Flon-143a and tetrafluoroethane, preferred are those comprising 40 to 5% by weight of the former and 60 to 95% by weight of the latter.
- chlorotetrafluoroethane for use in the invention are 2-chloro-1,1,1,2-tetrafluoroethane (Flon-124) and 1-chloro-1,1,2,2-tetrafluoroethane (Flon-124a).
- tetrafluoroethane for use herein are 1,1,1,2-tetrafluoroethane (Flon-134a) and 1,1,2,2-tetrafluoroethane (Flon-134).
- Flon-124 and Flon-124a can achieve a similar degree of effect and thus can be replaced by each other or mixed with each other in use. This can be done in respect of Flon-134a and Flon-134.
- the refrigerants of the invention are smaller in the ratio of specific heat and lower in the temperature of gas discharged from the compressor than Flon-22 and are consequently suitable for use as a cooling medium for a refrigeration cycle using a relatively high temperature as in an air-conditioning equipment of the heat pump type.
- the composition of the invention is a non-azeotropic composition.
- a single compound or an azeotrope is vaporized at a constant temperature in an evaporator because of its evaporation done under constant pressure, whereas a non-azeotropic composition has a low temperature at the inlet of the evaporator and a high temperature at the outlet thereof.
- a fluid to be cooled is caused to flow in countercurrent to the refrigerant in the evaporator to undergo heat exchange and thus has a temperature gradient along the flow direction even if the refrigerant is vaporized at a constant temperature.
- the refrigerant of the non-azeotropic composition according to the invention can be rendered close in temperature to the temperature gradient of the fluid to be cooled in the evaporator, so that the refrigeration efficiency, namely the coefficient of performance, can be enhanced.
- Refrigerants were prepared by mixing together Flon-143a and Flon-124 in the various proportions shown below in Table 1 (weight ratio).
- a refrigerator was operated with an output of 1 hp. using the refrigerants of the composition shown in Table 1.
- Each refrigerant started condensation at 50° C. in a condenser and had a temperature of 0° C. in the inlet of the evaporator with superheat of 5° C.
- Table 2 below shows (I) the maximum evaporating temperature (°C), (II) refrigerating capacity (kcal/m 3 ), (III) coefficient of performance and (IV) discharge temperature (°C) at the compressor.
- Table 2 also shows the results achieved by using Flon-143a alone (Comparison Example 1).
- FIG. 1 indicates a graph illustrating the relationship between the proportions of Flon-143a and Flon-124 and the coefficient of performance (curve A).
- Table 2 and FIG. 1 reveal that the refrigerants of the present invention have outstanding properties.
- Table 4 shows (I) the maximum evaporating temperature (°C), (II) refrigerating capacity (kcal/m 3 ), (III) coefficient of performance and (IV) discharge temperature (°C) at the compressor in respect of the refrigerants.
- FIG. 2 indicates a graph illustrating the relationship between the proportions of Flon-143a and Flon-134a and the coefficient of performance (curve B).
Abstract
The present invention provides a refrigerant comprising 1,1,1-trifluoroethane and either chlorotetrafluoroethane or tetrafluoroethane.
Description
This invention relates to a working fluid for a refrigerator, which is called a refrigerant.
Refrigerants heretofore known include chlorofluoroalkanes, fluoroalkanes, azeotropic compositions thereof and other materials having a similar composition. These are generally called flons or flon refrigerants. Among them, chiefly used at present are dichlorodifluoromethane (hereinafter referred to as "Flon-12"), chlorodifluoromethane (hereinafter called "Flon-22") and the like. In recent years, however, it has been pointed out that certain kinds of flons released into the atmosphere would destroy the stratospheric ozone layer, thereby inflicting a serious adverse influence on the ecosystem including humans on the earth. Although said proposition may have yet to be scientifically and completely established, there is a tendency toward the control, under an international agreement, of use and production of flons which are likely to destroy the ozone layer. The flons to be controlled include Flon-12. With the spread of refrigerators and air-conditioning systems, the control over the use and production of flons, which are in greater demand year after year, greatly affects our residential environment and the current social framework as a whole. In consequence, there is an urgent demand for development of refrigerants having a high refrigerating performance, particularly a high coefficient of performance. It may be possible to offer 1,1,1-trifluoroethane (Flon-143a) as flons free of ozone layer-destroying risks but has the defect of being low in coefficient of performance.
The term "coefficient of performance" used herein means the ratio of refrigerating capacity to compressing work. The refrigerating capacity is the quantity of heat removed per a unit time from the substances being cooled, and the compressing work is the work volume achieved per a unit time by power for operating the refrigerator. Accordingly the coefficient of performance corresponds to the refrigeration efficiency of the refrigerant.
We conducted extensive research to develop novel refrigerants which have a high coefficient of performance and which, when released into the atmosphere, would exert little influence on the ozone layer. Our research revealed that a refrigerant comprising 1,1,1-trifluoroethane (Flon-143a) and chlorotetrafluoroethane or tetrafluoroethane can exhibit a higher coefficient of performance than Flon-143a.
The present invention, therefore, provides a refrigerant comprising 1,1,1-trifluoroethane and either chlorotetrafluoroethane or tetrafluoroethane.
FIGS. 1 and 2 show graphs illustrating the refrigerating performance of the refrigerants according to the present invention.
Preferred refrigerant compositions of the invention are those comprising 90 to 5% by weight of 1,1,1-trifluoroethane and 10 to 95% by weight of either chlorotetrafluoroethane or tetrafluoroethane. Refrigerants containing chlorotetrafluoroethane or tetrafluoroethane in the foregoing ratio have a noticeably improved coefficient of performance compared with Flon-143a singly used. A particularly preferable mixing ratio is as follows. Of refrigerants composed of Flon-143a and chlorotetrafluoroethane, preferred are those comprising 70 to 5% by weight of the former and 30 to 95% by weight of the latter. Of refrigerants composed of Flon-143a and tetrafluoroethane, preferred are those comprising 40 to 5% by weight of the former and 60 to 95% by weight of the latter.
Examples of chlorotetrafluoroethane for use in the invention are 2-chloro-1,1,1,2-tetrafluoroethane (Flon-124) and 1-chloro-1,1,2,2-tetrafluoroethane (Flon-124a). Examples of tetrafluoroethane for use herein are 1,1,1,2-tetrafluoroethane (Flon-134a) and 1,1,2,2-tetrafluoroethane (Flon-134). Among the compositions of the invention, Flon-124 and Flon-124a can achieve a similar degree of effect and thus can be replaced by each other or mixed with each other in use. This can be done in respect of Flon-134a and Flon-134.
The refrigerants of the invention are smaller in the ratio of specific heat and lower in the temperature of gas discharged from the compressor than Flon-22 and are consequently suitable for use as a cooling medium for a refrigeration cycle using a relatively high temperature as in an air-conditioning equipment of the heat pump type.
The composition of the invention is a non-azeotropic composition. Generally a single compound or an azeotrope is vaporized at a constant temperature in an evaporator because of its evaporation done under constant pressure, whereas a non-azeotropic composition has a low temperature at the inlet of the evaporator and a high temperature at the outlet thereof. On the other hand, a fluid to be cooled is caused to flow in countercurrent to the refrigerant in the evaporator to undergo heat exchange and thus has a temperature gradient along the flow direction even if the refrigerant is vaporized at a constant temperature. In other words, a temperature difference between the refrigerant and the fluid to be cooled diminishes in the evaporator as the fluid flows forwardly. In use, the refrigerant of the non-azeotropic composition according to the invention can be rendered close in temperature to the temperature gradient of the fluid to be cooled in the evaporator, so that the refrigeration efficiency, namely the coefficient of performance, can be enhanced.
The features of the present invention will be clarified below with reference to the following Examples and Comparison Example.
Refrigerants were prepared by mixing together Flon-143a and Flon-124 in the various proportions shown below in Table 1 (weight ratio).
TABLE 1
______________________________________
Flon-143a
Flon-124
______________________________________
Comp. Example 1 100 0
Example 1 90 10
Example 2 80 20
Example 3 60 40
Example 4 40 60
Example 5 20 80
Example 6 5 95
______________________________________
A refrigerator was operated with an output of 1 hp. using the refrigerants of the composition shown in Table 1. Each refrigerant started condensation at 50° C. in a condenser and had a temperature of 0° C. in the inlet of the evaporator with superheat of 5° C. Table 2 below shows (I) the maximum evaporating temperature (°C), (II) refrigerating capacity (kcal/m3), (III) coefficient of performance and (IV) discharge temperature (°C) at the compressor.
Table 2 also shows the results achieved by using Flon-143a alone (Comparison Example 1).
TABLE 2
__________________________________________________________________________
Maximum evapora-
Refrigerating
Coefficient
Discharge
ting temperature
capacity
of perform-
temperature
(°C.)
(kcal/m.sup.3)
ance (°C.)
(I) (II) (III) (IV)
__________________________________________________________________________
Comp. Example 1
0.0 647 3.55 62.9
Example 1
1.7 636 3.82 62.2
Example 2
3.3 621 4.09 61.2
Example 3
5.7 578 4.64 58.8
Example 4
6.8 509 5.03 56.1
Example 5
5.6 401 4.99 53.3
Example 6
2.0 293 4.47 50.8
__________________________________________________________________________
FIG. 1 indicates a graph illustrating the relationship between the proportions of Flon-143a and Flon-124 and the coefficient of performance (curve A).
Table 2 and FIG. 1 reveal that the refrigerants of the present invention have outstanding properties.
The properties of refrigerants were investigated in the same manner as in Examples 1 to 6 with the exception of using the refrigerants prepared by mixing together Flon-143a and Flon-134a in the various proportions (weight ratio) shown below in Table 3.
TABLE 3
______________________________________
Flon-143a
Flon-134a
______________________________________
Example 7 90 10
Example 8 80 20
Example 9 60 40
Example 10 40 60
Example 11 20 80
Example 12 5 95
______________________________________
Table 4 shows (I) the maximum evaporating temperature (°C), (II) refrigerating capacity (kcal/m3), (III) coefficient of performance and (IV) discharge temperature (°C) at the compressor in respect of the refrigerants.
FIG. 2 indicates a graph illustrating the relationship between the proportions of Flon-143a and Flon-134a and the coefficient of performance (curve B).
TABLE 4
__________________________________________________________________________
Maximum evapora-
Refrigerating
Coefficient
Discharge
ting temperature
capacity
of perform-
temperature
(°C.)
(kcal/m.sup.3)
ance (°C.)
(I) (II) (III) (IV)
__________________________________________________________________________
Example 7
0.6 640 3.68 62.8
Example 8
1.1 630 3.81 62.8
Example 9
1.8 602 4.04 62.4
Example 10
2.0 561 4.18 62.2
Example 11
1.5 508 4.24 61.8
Example 12
0.5 458 4.19 61.7
__________________________________________________________________________
Claims (3)
1. A working fluid for refrigerator consisting essentially of 90 to 5% by weight of 1,1,1-trifluoroethane and respectively 10 to 95% by weight of either chlorotetrafluoroethane or tetrafluoroethane.
2. A working fluid according to claim 1 which consists essentially of 70 to 5% by weight of 1,1,1-trifluoroethane and respectively 30 to 95% by weight of chlorotetrafluoroethane.
3. A working fluid according to claim 1 which consists essentially of 40 to 5% by weight of 1,1,1-trifluoroethane and respectively 60 to 95% by weight of tetrafluoroethane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62238441A JPH075880B2 (en) | 1987-09-21 | 1987-09-21 | Coolant |
| JP62-238441 | 1987-09-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5035823A true US5035823A (en) | 1991-07-30 |
Family
ID=17030269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/362,385 Expired - Lifetime US5035823A (en) | 1987-09-21 | 1988-09-21 | Refrigerant compositions of 1,11-trifluoroethane |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5035823A (en) |
| EP (1) | EP0349647A1 (en) |
| JP (1) | JPH075880B2 (en) |
| WO (1) | WO1989002456A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5294359A (en) * | 1992-02-03 | 1994-03-15 | Alliedsignal Inc. | Refrigerant compositions |
| US5474695A (en) * | 1991-10-09 | 1995-12-12 | D'elf Atochem S.A. | Mixtures of 1,1,1-trifluoroethane, perfluoropropane and propane, and their applications as refrigerant fluids, as aerosol propellants or as blowing agents for plastic foams |
| US5723429A (en) * | 1994-03-11 | 1998-03-03 | E. I. Du Pont De Nemours And Company | Azeotropic or azeotrope-like compositions of tetrafluoroethane and chlorotetrafluoroethane |
| US6054064A (en) * | 1994-07-11 | 2000-04-25 | Solvay (Societe Anonyme) | Refrigerant of 1,1-difluoroethylene |
| US6261472B1 (en) * | 1996-11-04 | 2001-07-17 | E. I. Du Pont De Nemours And Company | Azeotrope-like compositions containing fluoroethane |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03258888A (en) * | 1990-03-07 | 1991-11-19 | Daikin Ind Ltd | Refrigerant |
| JP2792191B2 (en) * | 1990-04-04 | 1998-08-27 | ダイキン工業株式会社 | Coolant |
| US5277834A (en) * | 1990-07-26 | 1994-01-11 | E. I. Du Pont De Nemours And Company | Near-azeotropic blends for use as refrigerants |
| ATE153367T1 (en) * | 1990-07-26 | 1997-06-15 | Du Pont | QUASI-AZEOTROPIC MIXTURES FOR USE AS REFRIGERANTS |
| FR2686092B1 (en) * | 1992-01-13 | 1994-09-16 | Atochem Elf Sa | MIXTURES OF 1,1,1-TRIFLUOROETHANE AND PERFLUOROPROPANE AND THEIR APPLICATIONS AS REFRIGERANTS, AS AEROSOL PROPELLERS OR AS PLASTIC FOAM EXPANSION AGENTS. |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3377287A (en) * | 1965-06-04 | 1968-04-09 | Du Pont | Refrigerant compositions |
| US4224795A (en) * | 1978-12-26 | 1980-09-30 | Allied Chemical Corporation | Method for converting heat energy to mechanical energy with monochlorotetrafluoroethane |
| US4303536A (en) * | 1980-12-29 | 1981-12-01 | Allied Corporation | Nonazeotropic refrigerant composition containing monachlorodifluoromethane, and method of use |
| JPS63305185A (en) * | 1987-06-05 | 1988-12-13 | Asahi Glass Co Ltd | Working medium mixture |
| JPS63308084A (en) * | 1987-06-09 | 1988-12-15 | Asahi Glass Co Ltd | Operation medium mixture |
| JPS63308085A (en) * | 1987-06-09 | 1988-12-15 | Asahi Glass Co Ltd | Operation medium mixture |
| US4810403A (en) * | 1987-06-09 | 1989-03-07 | E. I. Du Pont De Nemours And Company | Halocarbon blends for refrigerant use |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7708731A (en) * | 1976-08-13 | 1978-02-15 | Montedison Spa | PROCESS FOR THE PREPARATION OF NEW DRIVER COMPOSITIONS FOR AEROSOLS. |
| JPS58171494A (en) * | 1982-03-31 | 1983-10-08 | Daikin Ind Ltd | Working fluid for rankine cycle |
-
1987
- 1987-09-21 JP JP62238441A patent/JPH075880B2/en not_active Expired - Lifetime
-
1988
- 1988-09-21 WO PCT/JP1988/000952 patent/WO1989002456A1/en not_active Application Discontinuation
- 1988-09-21 US US07/362,385 patent/US5035823A/en not_active Expired - Lifetime
- 1988-09-21 EP EP88908343A patent/EP0349647A1/en not_active Ceased
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3377287A (en) * | 1965-06-04 | 1968-04-09 | Du Pont | Refrigerant compositions |
| US4224795A (en) * | 1978-12-26 | 1980-09-30 | Allied Chemical Corporation | Method for converting heat energy to mechanical energy with monochlorotetrafluoroethane |
| US4303536A (en) * | 1980-12-29 | 1981-12-01 | Allied Corporation | Nonazeotropic refrigerant composition containing monachlorodifluoromethane, and method of use |
| JPS63305185A (en) * | 1987-06-05 | 1988-12-13 | Asahi Glass Co Ltd | Working medium mixture |
| JPS63308084A (en) * | 1987-06-09 | 1988-12-15 | Asahi Glass Co Ltd | Operation medium mixture |
| JPS63308085A (en) * | 1987-06-09 | 1988-12-15 | Asahi Glass Co Ltd | Operation medium mixture |
| US4810403A (en) * | 1987-06-09 | 1989-03-07 | E. I. Du Pont De Nemours And Company | Halocarbon blends for refrigerant use |
Non-Patent Citations (2)
| Title |
|---|
| Research Disclosure, Abstract 15402, "Hydrogen-Containing Chlorofluorocarbons as Refrigerants", Feb. 1977. |
| Research Disclosure, Abstract 15402, Hydrogen Containing Chlorofluorocarbons as Refrigerants , Feb. 1977. * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5474695A (en) * | 1991-10-09 | 1995-12-12 | D'elf Atochem S.A. | Mixtures of 1,1,1-trifluoroethane, perfluoropropane and propane, and their applications as refrigerant fluids, as aerosol propellants or as blowing agents for plastic foams |
| US5294359A (en) * | 1992-02-03 | 1994-03-15 | Alliedsignal Inc. | Refrigerant compositions |
| US5723429A (en) * | 1994-03-11 | 1998-03-03 | E. I. Du Pont De Nemours And Company | Azeotropic or azeotrope-like compositions of tetrafluoroethane and chlorotetrafluoroethane |
| US6054064A (en) * | 1994-07-11 | 2000-04-25 | Solvay (Societe Anonyme) | Refrigerant of 1,1-difluoroethylene |
| US6261472B1 (en) * | 1996-11-04 | 2001-07-17 | E. I. Du Pont De Nemours And Company | Azeotrope-like compositions containing fluoroethane |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0349647A4 (en) | 1989-08-22 |
| WO1989002456A1 (en) | 1989-03-23 |
| JPH075880B2 (en) | 1995-01-25 |
| EP0349647A1 (en) | 1990-01-10 |
| JPS6479199A (en) | 1989-03-24 |
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